Electrochemical and thermal digestion of organic molecules

ABSTRACT

Various examples are provided for electrochemical digestion of organic molecules. In one example, among others, a method includes providing a fluid mixture including organic molecules to a reaction vessel including at least one current distribution part suspended within the fluid mixture. At least a portion of the current distribution part is coated with nano catalytic powders. Current flow can be controlled through the fluid mixture to heat the fluid mixture and simultaneously cause electrolysis of the fluid mixture. In another example, a device includes a pipe section surrounding a fluid mixture including organic molecules, a current distribution part positioned within the pipe section and suspended in the fluid mixture, and an electrical coupling assembly configured to provide an electrical potential to the current distribution part for heating and electrolysis of the fluid mixture. At least a portion of the current distribution part is coated with nano catalytic powders.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No. 14/908,744, filed Jan. 29, 2016, which is the 35 U.S.C. § 371 national stage application of PCT Application No. PCT/US2014/048625, filed Jul. 29, 2014, which claims priority to and the benefit of, U.S. Provisional Patent Application entitled “ELECTROCHEMICAL AND THERMAL DIGESTION OF ORGANIC MOLECULES” having Ser. No. 61/859,450, filed Jul. 29, 2013, all of which are hereby incorporated by reference in their entireties.

This application is related to U.S. patent application entitled “Electrochemical Digestion of Organic Molecules” having Ser. No. 13/630,776, filed Sep. 28, 2012 and U.S. patent application entitled “Electrochemical Processing of Fluids” having Ser. No. 12/890,659, filed Sep. 25, 2010, both of which are hereby incorporated by reference in their entirety.

BACKGROUND

Presently, organic molecules are broken down, or digested, using expensive enzymes and/or microbes or by driving a high pressure water slurry of the organic molecules above 375° C. to spontaneously break down the molecules. This process is called “supercritical fluid” method where the temperature and pressure are at a point where a distinct liquid and gas phases do not exist. Both methods work well, but are expensive to achieve. The first has a high cost of enzymes or microbes and the second has a high-energy cost to heat the water slurry.

BRIEF DESCRIPTION OF THE DRAWINGS

Many aspects of the present disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.

FIG. 1 is an illustration of a portion of a cellulose molecule.

FIG. 2 is a cross-sectional view of an example of a circular reaction vessel in accordance with various embodiments of the present disclosure.

FIGS. 3A and 3B are plots of examples of wave shapes applied to electrodes of a reaction vessel of FIGS. 2, 5, and 8 in accordance with various embodiments of the present disclosure.

FIG. 4A is a graph of an example of iron corrosion versus frequency of a wave shape applied to the reaction vessel of FIG. 2 in accordance with various embodiments of the present disclosure.

FIG. 4B is a graph of an example of degradation of starch as a function of frequency applied to the reaction vessel of FIG. 2 in accordance with various embodiments of the present disclosure.

FIG. 5 is a cross-sectional view of an example of a single cell planer reaction vessel in accordance with various embodiments of the present disclosure.

FIGS. 6A and 6B are photographs of examples of electrodes of a reaction vessel of FIGS. 5 and 8 in accordance with various embodiments of the present disclosure.

FIG. 7A is a polarization curve for a planer reaction vessel of FIG. 6 with a square cell in accordance with various embodiments of the present disclosure.

FIGS. 7B and 7C are plots illustrating examples of coating effects in accordance with various embodiments of the present disclosure.

FIG. 8 is a cross-sectional view of an example of a four-cell planer reaction vessel in accordance with various embodiments of the present disclosure.

FIG. 9 is a photograph of an example of an electrode of a multi-cell reaction vessel of FIG. 8 in accordance with various embodiments of the present disclosure.

FIG. 10 is a graphical representation of an example of an electrochemical digestion system including a reaction vessel of FIGS. 2, 5, and 8 in accordance with various embodiments of the present disclosure.

FIG. 11 is a cross sectional view illustrating an example of a heating system in accordance with various embodiments of the present disclosure.

FIG. 12 includes perspective views of examples of several current distribution parts that can be used in the heating system of FIG. 1 in accordance with various embodiments of the present disclosure.

FIG. 13 includes perspective views of examples of various configurations of current distribution parts of FIG. 12 for inclusion in the heating system of FIG. 1 in accordance with various embodiments of the present disclosure.

FIGS. 14-16 illustrate examples of configurations of current distribution parts of FIG. 12 in a heating system in accordance with various embodiments of the present disclosure.

FIG. 17 is a graphical representation of an example of a continuous flow heating system in accordance with various embodiments of the present disclosure.

FIGS. 18 and 19 illustrate examples of heating systems including a central electrode in accordance with various embodiments of the present disclosure.

FIG. 20 includes cross sectional views of examples of heating plates of current distribution parts of FIGS. 12-16 including nano catalysts in accordance with various embodiments of the present disclosure.

FIGS. 21A-21C are various views of an example of a current distribution part including concentric tubes in accordance with various embodiments of the present disclosure.

FIG. 22 includes cross sectional views of examples of monopolar and bipolar electrodes including nano catalysts in accordance with various embodiments of the present disclosure.

FIGS. 23A-23E are various views of an example of interleaved current distribution parts in accordance with various embodiments of the present disclosure.

DETAILED DESCRIPTION

Disclosed herein are various examples related to electrochemical digestion of organic molecules. Reference will now be made in detail to the description of the embodiments as illustrated in the drawings, wherein like reference numbers indicate like parts throughout the several views.

The breakdown of long-chain organic molecules may be accomplished electrochemically by passing an electrolyte including the organic molecules between energized electrodes that include a reactive surface. A varying voltage may be applied to the electrodes to produce singlet oxygen to decompose the organic molecules. When water is electrolyzed, diatomic hydrogen is generated from the moment it is split from water by: 2H₂O+2e⁻→H₂+2OH⁻. However, the oxygen is liberated as singlet oxygen (also called a “nascent oxygen” or “atomic oxygen”) by the equation:

2OH⁻=½O₂+H₂O+2e⁻.

The singlet oxygen may remain for several milliseconds or more before combining with another singlet oxygen to form the stable diatomic oxygen molecule O₂. In some cases, the singlet oxygen may remain for as long as a tenth of a second or more. If the atom reaches another reactive atom such as, e.g., carbon, hydrogen or oxygen within an organic molecule, it can react with that molecule, fracturing the long chain. Organic molecules such as, e.g., cellulose or proteins may be decomposed by reacting with the singlet oxygen. In the case of cellulose, which is composed of thousands of glucose rings, it will break this long chain into smaller fragments. When the singlet oxygen remains in the electrolyte for an extended period of time, the singlet oxygen can continue to react with the organic molecules as the electrolyte flows out of between the electrodes.

Organic molecules may include, e.g., cellulose, hemicellulose, lignin, starch (e.g., amylose and amylopectin) algae (e.g., for lipid extraction), viruses and bacterium for decontamination, etc. FIG. 1 illustrates a portion of a cellulose molecule 100. A cellulose molecule includes up to tens of thousands of these six-carbon glucose molecules 102 connected with an oxygen atom 104. It seems likely that it is the oxygen that is being attacked since it is not in the stable ring. The oxygen may be the atom attacked by the hydroxyl or the singlet oxygen since it is oxygen that links the many sugar rings in the cellulose molecule, making it more exposed than the atoms within the organic ring. For example, the singlet oxygen may react with the glucose-bonding oxygen 104, breaking the long chain into smaller segments and ultimately into glucose 102. The singlet atom may attack any of the three reactive elements present in an organic molecule: a carbon to form CO and CO₂, hydrogen to form H₂O or another singlet oxygen to form diatomic oxygen gas. The hydrogen may combine with any lipids or oils in a classic hydrogenation reaction.

The organic molecules may be decomposed very efficiently when the proper waveform (or wave shape) is applied to the electrodes of a reaction vessel. The process may also be used to kill pathogens in microbiology laboratories or to render the lipids from the cell vesicles in algae. Shortening of the chain, removing excess oxygen atoms, breaking cell walls, and/or destroying organisms may be carried out on organic molecules such as, but not limited to, cellulose, hemicellulose, lignin, starch (e.g., amylose and amylopectin) algae (e.g., for lipid extraction), viruses and bacterium for decontamination, etc. Any organic compound may be attacked using this method. Applications may include but are not limited to:

-   -   Increasing the energy density of organic materials such as,         e.g., cellulosic and lignin materials, among others, by reducing         the oxygen content in component chains;     -   Breaking the thousands of carbon cellulose chain into C5 or C6         sugars for cellulosic ethanol production;     -   Breaking open (or lyse) the vesicle wall of algae containing         lipids for bio-fuels;     -   Destroying biological agents such as viruses and bacterium         through oxidation of their protein membranes, etc.; and/or     -   Digesting organic molecules such as, e.g., cellulose,         polysaccharides, lignin, hemicellulose, proteins, algae,         viruses, bacterium and/or solids suspended in wastewater.

The reaction vessel may include one or more cells defined by electrodes where electrolyte including organic molecules can be disposed between the electrodes for electrochemical digestion. The reactive surface of an electrode may include, e.g., a metallic current collector coated with a plurality of nano powders to catalyze the reaction to increase the surface area. In other implementations, the electrodes may include, but are not limited to: metallic electrodes with some amount of platinum metal plated or added such as nano powders on the surface; titanium electrodes with a flash plating of platinum; or electrodes catalyzed with noble metals such as, e.g., platinum, ruthenium or palladium and/or mixtures or alloys thereof. In some cases, the noble metal catalysts may be mixed or alloyed with other transition metals.

In various embodiments, a high-surface area electrode may include three components. The first component may be a substrate such as a plate or other structure having a regular or complex geometry and having a smooth or rough surface and including of transition metals including among others, nickel, iron, stainless steel, or silver. The first component may be defined by a reticular structure, a plate, a random textile, channeled, dendritic, foam, or other self-similar patterned or unpatterned structure with internal channels and/or external grooves and/or pits, spines, fins, or any kind of structure that permits fluids or fluid components to reach a surface or surfaces thereof, including a surface of a material layered on the substrate, either by convection, advection or diffusion. The second component may include one or more transition metals such as, e.g., nickel, gold, silver and/or other metals attached to (or disposed on) the first component, for example by electroplating. The third component may include metal particles such as, e.g., nano-sized metal particles and/or mixed nano-micron sized particles of transition metals including, but not limited to, iron, tin, nickel, silver, manganese, cobalt and alloys and oxides of these metals.

The third component may be partially embedded in the second component and may principally include nano and/or micron sized particles partially embedded in the second component but exposed such that when the completed electrode is immersed in the electrolyte, the third component is in intimate contact with the electrolyte. The third component may be partially covered by the second component but, due to the second component's overlying the third component closely, so conforming to the third component size and shape that the third component imparts a roughness to the surface of the second component that is responsive to the size and shape of the third component. This electrode may be used in electrochemical devices, including, but not limited to, hydrogen-generating electrodes in a water electrolyzer system, organic digestion systems and/or fuel cells. The very high surface area, with a high percentage of surface atoms, may render the surface highly catalytic to the splitting of water molecules in the presence of electrical energy.

Nano catalysts may be attached to current collecting surfaces of the electrode. By electroplating the surface with a metallic material, nano particles are entrapped within the electroplated metallic layer to permanently adhere the particles to that surface. The catalysts may include metals, metal oxides, or a mixture of metals, alloys and/or their oxides. Noble metals may also be included to catalyze or enhance the reaction. The resulting electrode can be arranged to produce an apparatus with a very high rate and high efficiency of water electrolysis. A method for the coating of an electrode is described in “Electrochemical Devices, Systems and Methods” (U.S. Patent App. Pub. 2011/0114496, published May 19, 2011, and PCT Pub. WO 2010/009058, published Jan. 21, 2010), both of which are hereby incorporated by reference in their entirety.

One way to coat an electrode with nano catalysts is where the particles exhibit very low impedance while allowing them to freely interact with the liquid boundary layer for electrochemical activity. The nano catalytic powders are entrapped within a plating substrate such as, e.g., nickel, copper, tin, silver and/or gold. The coating may be applied on all surfaces inside and outside of a complex porous shape such as, e.g., a foam surface. A uniform coating on all internal and external surfaces of the porous structure can extend the reactive surface area, leaving the particles well exposed with very low impedance at the reaction sites. The foam surface may be welded to a solid base plate prior to coating. The loading of nano powders may be increased from 1% of the bath weight to 5% to 10% of the plating solution weight. The pH may also be lowered from a pH of 4 to a pH of 2. The plating is first applied with a short burst of current in a forward direction, entrapping the powders under the coating. A rest period allows for ionic diffusion to rebalance the ionic concentrations. A reverse pulse is than applied to strip the plated metal from the top of each nano particle. The sequence may be repeated to increase the amount of nano catalytic powder coating the electrode. For example, in one implementation a 14 cm² foam electrode was coated by applying +30 Amps for about 0.5 mSec; 0.0 Amps for about 9.5 mSec; −10 Amps for about 0.75 mSec; 0.0 Amps for about 0.25 mSec; and repeating the cycle for about 48.88 minutes to give 2000 ASec of coating. The short forward pulses attach the powders to the external and internal surfaces and the reverse pulses strip the nickel off of the nano powders, leaving them exposed to the boundary layer.

The coated electrode may be used for electrolysis of water to produce hydrogen and/or oxygen at an efficient and high rate. The electrode may function as an anode or a cathode. The singlet oxygen produced on the anode of the electrolyzer may be used to degrade and digest organic molecules and the hydrogen produced at the cathode of the cell hydrolyzes any lipids present in the electrolyte fluid. The energy to do this is low as compared to the previous methods. Other examples of electrode designs include, but are not limited to, platinum particles adhered to a titanium plate, nano catalyst(s) adhered to stainless steel plate, a flat metallic surface of transition metal(s), nano catalyst(s) adhered to a two-dimensional surface or to a three-dimensional surface such as e.g., a metallic foam or a metallic sheet or foam that is corrugated, folded, or patterned.

Referring to FIG. 2, shown is a cross-sectional view of an example of a circular reaction vessel 200 including an outer electrode 202 and an inner electrode 204. The single cell reaction vessel 200 of FIG. 2 may be made from end plates 206 and 208 of, e.g., stainless steel 316 (SS316) and inner insulators 210 and 212 of, e.g., ⅜″ sintered Teflon®. The sidewalls may be the outer electrode 202 (e.g., a 4-inch ID SS316 tube) and the inner electrode 204 (e.g., an 1-inch OD SS316 tube) of approximately the same height. For example, the sidewalls may be about 2 inches tall. Electrical contact may be made via contact rods 214 and 216. Also included in the example of FIG. 2 are Lugen's electrode tubes 218 and 220 for continuous reference electrode monitoring of the reaction vessel's electrodes during operation. In some implementations, pure zinc wire is used as a reference metal. The reaction vessel may be held together using e.g., eight 3 inch long, 5/16″ SS316 bolts 222 and nuts, each tightened to a torque of about 20 inch-pounds. Inlet and outlet connections can be included to allow a fluid such as an electrolyte including organic molecules to fill the chamber between the outer electrode 202 and inner electrode 204. In the example of FIG. 2, a single cell 224 defined by the outer and inner electrodes 202 and 204 contains the electrolyte. No separator is included between the electrodes 202 and 204 and thus separate cathodic and anodic chambers are not formed, which simplifies the design of the reaction vessel 200. Dimensions of the reaction vessel 200 may be varied to increase processing capabilities.

Organic molecules may be decomposed within the reaction vessel 200. With an electrolyte including the organic molecules disposed within the cell 224 of the reaction vessel 200, a varying voltage can be applied between the inner and outer electrodes 204 and 202 to produce the singlet oxygen to decompose the organic molecules.

FIG. 3 show examples of the voltage wave shape applied to the electrodes 202/204. The wave-shape of the applied voltage may be a square wave, sine wave, or other appropriate alternating wave shape. FIG. 3A illustrates a square wave at 100% duty cycle. Operation at a low frequency was found to improve the decomposition of polysaccharides, but other frequencies and/or flow rates may provide the best results for other organic molecules. The voltage wave shape may be applied in a range of about 100 Hz or lower, a range of about 10 Hz or lower, a range of about 1 Hz or lower, a range of about 0.1 Hz or lower, a range of about 10 mHz or lower, a range of about 1 mHz or lower, or a range of about 0.1 mHz or lower.

Various experiments were performed using cornstarch to verify the digestion of organic molecules. The electrolyte can be produced using an easily ionized compound such as, e.g., sodium chloride (NaCl), potassium hydroxide (KOH), sodium hydroxide (NaOH), hydrochloric acid (HCl), among many others. In some implementations, concentrations of the ionized compound may be in the range of about 5% or less, in the range of about 2% or less, in the range of about 1% or less, in the range of about 0.75% or less, or in the range of about 0.5% or less. The electrolyte may be prepared by mixing the ionized compound solution, followed by a slow heating to about 100° C. and subsequent cooling while continuously stirring the solution. If glucose is added, it may be added to the hot electrolyte before cooling. The electrolyte fluid allows the charge to be carried between the electrodes. In some implementations, the reaction vessel 200 of FIG. 2 held a 1% KOH electrolyte solution including about 300 ml of 1% cornstarch. In other implementations, the electrolyte inside the reaction vessel was a 1% NaCl electrolyte solution including 1% starch and about 0.3% glucose. In the experiments, there was no circulation except natural convection produced by gas and/or heat generation by the reaction.

The concentration of starch in solution was determined based upon the colorimetric method using the well-known starch iodine reaction. The electrolyte was used as a detector solution consisting of 0.35 cc of 1% Iodine (I) and 0.35 cc 1% potassium iodide (KI) in water. The maximum absorption wavelength was found to be 620 nm. A calibration curve was developed using serial dilutions from the 1% starting point giving the relationship of:

Percent starch=−0.0065*LN(%T)−0.0001

where LN(%T) is the natural logarithm of the percent of 620 nm light transmitted through a tube of fluid within the spectrophotometer.

Using the 50 Hz, 50% duty square wave of FIG. 3, 24-hour starch digestion experiments were performed using the circular reaction vessel 200 with four different electrode materials: smooth SS316, Ni Foam, smooth SS316 coated with nano iron (nFe), and foam coated with a tri-nano recipe (foam tri). The Ni Foam was INCO foamed nickel with 1450 g/m² density and 4.5 mm thick and a pore size of about 600 um diameter. Digestion with the Ni Foam was more effective than digestion with the smooth SS316. This may be due to the increase in surface area. Coating the smooth SS316 with nano iron (nFe) improved the digestion. The foam coated with a tri-nano recipe of nFe, nCo and nSn showed the highest amount of digestion proving the feasibility of the use of the nano coated electrodes as part of an organic digester. Other formulations of nano powders may also be used.

As the amount of digestion increased, the lower the temperature rise of the reaction vessel 200 (FIG. 2). This indicates that even though the input energy remained the same for the experiments, when digestion was being accomplished less of that energy was being dissipated as heat because of the additional electrochemical work being accomplished. This may be related to an increase in the formation of singlet oxygen, which may result from an increase in the electrode surface area. The use of circular electrodes 202/204 with dramatically different surface areas may also have affected the results. The surface area of outer and inner electrodes 202/204 varied by a factor of 3.5:1. The surface area ratio plays an electrochemical role where the inner electrode 204 is running at a current density that is 3.5 times higher than the outer electrode 202. The current density imbalance as the polarity swings from positive (anodic singlet oxygen generating with subsequent organic digestion) to negative (diatomic hydrogen generation with quenching effect) may limit the effectiveness of the circular design.

The effect of the formation of singlet oxygen on the electrode material was examined using its reaction with iron from the SS316. Referring to FIG. 4A, shown is a graph of iron corrosion versus applied frequency. The circular reaction vessel 200 of FIG. 2 containing a 1% NaCl electrolyte was used to study the corrosion of iron from SS316 as a function of the frequency of the applied voltage wave shape. All wave-shapes at the different frequencies were the 50% duty square wave illustrated in FIG. 2A except where a DC voltage was applied. Each experiment was run at 0.5 AHrs with a peak-to-peak voltage of 40 volts. To evaluate the effect on the nFe coating, a set of standard iron chloride concentrations was prepared to calibrate a spectrophotometer. It was determined that the maximum absorption (lowest light transmission) was achieved at 405 nanometers and a calibration curve was built at that wavelength. The resulting concentration was then converted to grams of iron/0.5 AHrs.

At DC, the singlet oxygen never sees the neutralizing hydrogen, so it attacks the iron vigorously. As the applied frequency is increased, hydrogen is delivered more quickly to the singlet site where it reacts, reforming a water molecule. As can be seen in FIG. 4A, the amount of corrosion is very low by 50 Hz and it is almost non-existent, dropping to nearly zero, by 100 Hz. At this point, the rapidly changing polarity causes the singlet oxygen to recombine with the hydrogen produced at the same site to form water. This suggests that the singlet oxygen remains in solution for about 12 milliseconds (mSec) or the time of an applied voltage wave shape at 80 Hz. It has either combined with another singlet oxygen to form diatomic oxygen or reacted with some available atom such as hydrogen or a metallic atom such as iron. Below 100 Hz, a race between reacting with the iron in the SS316 or the organic molecule is underway when using the 1% NaCl electrolyte. Above this frequency, digestion is unlikely because the singlet oxygen has not had enough time to react with the organic molecule. The preferred frequency, therefore, should be below 60 Hz.

As shown in FIG. 4A, metals like iron is exhibit a higher corrosion rate as the applied voltage frequency is lowered when using a NaCl electrolyte. This also shows the effect of the singlet oxygen on any other atom that is available to react with it. This may be compensated by utilizing a different electrolyte. For example, a 1% KOH electrolyte may be used instead. The KOH loading is a low enough to not have spontaneous degradation of organic molecules, but high enough (e.g., with a pH of 13) to allow good ion transport for the electrochemical reactions needed for organic degradation. The wave shape used was 100% duty cycle as shown in FIG. 3B.

Experiments were run using a 1% KOH electrolyte solution including 1% starch at room temperature. The experiments were carried out at various frequencies with a 100% duty cycle. FIG. 4B shows the degradation of starch as a function of the applied frequency, using the same galvanic charge and a 100% duty cycle. Performance improved as the frequency was lowered until about a 10 minute cycle (about 1.66 mHz) was reached, where the performance began to decrease again. As the applied voltage approached DC, performance was good.

Referring now to FIG. 5, shown is a cross-sectional view of an example of a single cell reaction vessel design including a planer reaction vessel 600 with parallel electrodes 602 on either side of the cell 604, which may be made of a variety of materials. Use of a flat-plate reaction vessel 600 with an inlet 606 and outlet 608 for filling and venting of the cell 604 resolved the current density imbalance between the electrodes 602. In one embodiment of the reaction vessel 600, the cell body 610 is composed of ⅜″ Noryl blocks, each with square outside dimensions of about 2 inches. A gasket 612 made of, e.g., soft Teflon may be used to seal the electrolyte within the cell 604 with an internal volume of about 28.5 ml. The electrodes 602 include two monofunctional electrodes. The electrodes 602 may include a substrate 614 (e.g., a stainless steel 316 plate) onto which is secured (e.g., welded) a porous metal component 616 (e.g., a section of nickel foam). Other metals such as, e.g., titanium or nickel may also be used. The porous metal component 616 may be nickel foam that is about 3.75 cm square (or about 14 cm²). In other embodiments, electrode sizes can range from about 100 cm² to about 1000 cm² or more. A mixture of nano catalysts (e.g., a tri-nano recipe of nano Co, Ni and Sn) may be adhered to the electrode 602 as describe above. Other catalysts such as, e.g., titanium, platinum, or other non-noble metal nano catalysts may be used. No separator is included between the electrodes 602 and thus separate cathodic and anodic chambers are not formed, which simplifies the design of the reaction vessel 600. Electrical contacts are also provided to couple to the power source for application of the voltage wave shape. Dimensions of the reaction vessel 600 may be varied to increase processing capabilities.

FIGS. 6A and 6B are pictures of examples of an electrode 602. The porous metal component 616 is spot welded to the substrate 614, which renders an active central portion surrounded by a solid low-corrosion current-collecting plate that extends to the sides of the reaction vessel 600. The substrate 614 may be made of, e.g., stainless steel, nickel, or other suitable material. The porous metal component 616 may be, e.g., nickel foam or other suitable material as discussed above. The shape may be square, rectangular, circular, polygonal or other shape as can be understood. Three-dimensional shapes may also be utilized to increase the surface area of the electrode 602. FIG. 6B illustrates a corrugated electrode, which increases the exposure of the reactive surface to the electrolyte in the cell. The porous metal component 616 may be nickel foam that is spot welded to a substrate 614 of nickel Dexmet material. A contact tab 618 for connection to the power source may be gold plated to improve conductivity.

Referring back to FIG. 5, during operation, electrolyte including the organic molecules may be passed through the reaction vessel 600 via the inlet and outlet connections 606/608 and the electrodes 602 are energized by a power source to digest the organic molecules. During the cycle in which electrode 602 a is negatively charged, hydrogen gas and hydroxyl ions are evolved from that electrode 602 a while consuming two water molecules and two electrons (2H₂O+2e⁻→2OH⁻+H₂). The hydroxyl molecule diffuses to the positive electrode 602 b where the hydroxyl ions liberate their electrons into the plate while creating a singlet oxygen (or nascent oxygen) and one water molecule (2OH⁻→½O₂+H₂O+2e⁻). The electrons exit into that positive electrode 602 b. The singlet oxygen breaks down the organic molecules as described above. The polarity of the electrodes 602 is alternated when driven by 100% duty cycle illustrated in FIG. 3B.

Referring now to FIG. 7A, shown is a plot illustrating the full cell voltage with respect to the current (or polarization curve) of the single cell reaction vessel of FIG. 5. Using the single cell device 600, precise polarization measurements were made using four different electrode configurations: SS316 (curve 702), Ni Foam (curve 704), SS316 Trinano (curve 706), and Trinano foam (curve 708). A 1% NaCl electrolyte was used with no organic molecules so the reaction product was simply hydrogen and singlet oxygen, which spontaneously recombined back to water. The driving currents were supplied at a 50 Hz, 50% duty cycle as illustrated in FIG. 3A. The slope of a polarization curve is resistance by Ohms Law (R=V/I). This impedance is both “real” impedance caused by electrolyte and the component resistance and “imaginary” impedance (also called reactance) caused by electrochemical efficiency and the double layer capacitance. All the “real” impedance is the same in the four lines shown, but the efficiency changes dramatically. The “real” impedance may be improved through design changes like electrode spacing, number of cells and total surface area.

As can be seen from FIG. 7A, the lower the voltage at any one current density, the higher the catalytic activity and the more efficient the electrochemical process. As electrochemical efficiency improves, the temperature rise should be lower because the temperature rise is driven by the wattage which is the product of the voltage times the applied current. As the voltage goes down, so does the wattage.

Electrochemical Impedance Spectroscopy (EIS) is a very useful technique to evaluate the activity of electrodes. An impedance scan provides a measurement of the total AC impedance as a function of the frequency applied. The lower the impedance, the higher the activity of the electrode. FIG. 7B is a Bode plot showing an example of the effect of the coating by comparing three electrodes in 33% KOH. Curve 710 corresponds to smooth stainless steel 316 (SS316), curve 712 corresponds to uncoated nickel foam and curve 714 corresponds to the foam coated with a trio of nano powders (tri-nano). The advantage of including the nano coating can be seen.

FIG. 7C shows Voltammogram curves for the same three electrodes (SS316=curve 716, Ni foam=curve 718, and tri-nano coated=curve 720) for both a cathodic (downward slope and hydrogen producing) and anodic (upward slope and oxygen producing) directions. In this type of scan, the voltage is very slowly driven from equilibrium to some endpoint while the current is allowed to float. The exposed surface area was 1 cm² and the electrolyte in this case was 33% KOH. The reference electrode is a pure zinc wire. The lower the applied voltage for a current density, the higher the electrochemical energy efficiency. Thus, a higher the current density at a given voltage is more energy efficient.

Notice that the horizontal axis is logarithmic, so the cathodic current density is two decades (100×) higher with the nano coating.

The effectiveness of the reaction vessel may be improved by utilizing a plurality of cells to increase the total electrode surface area. FIG. 8 shows an example of a four-cell reaction vessel 800. Electrolyte may flow in parallel through the cells 802 with the electrodes connected in electrical series. In one embodiment, the reaction vessel 800 has a surface area of 14 cm² per electrode. This gives a total of 112 cm² of electrode surface exposed to the circulating electrolyte. In other embodiments, electrode sizes can range from about 100 cm² to about 1000 cm² or more. In the example of FIG. 8, the reaction vessel 800 includes four cells 802 manifolded together both at the inlet 804 and the outlet 806. The inlet and outlet ports 804 and 806 may be, e.g., a set of ⅛″ NPT “quick connect” hose fittings. The cells 802 may be within a cell body 808 composed of, e.g., Noryl blocks and gaskets 810 made of, e.g., soft Teflon. The electrodes include two monofunctional electrodes on each end 812 & 814, which function as either an anode or a cathode based upon the applied voltage, and three bifunctional electrodes 816 in the interior of the cells 802, which function as an anode on one side of the electrode 816 and a cathode on the other side of the electrode 816 depending upon the function of electrodes 812/814. The electrodes 812/814/816 may be built of a stainless steel 316 plate 818 onto which is welded nickel foam 820 such as, e.g., the electrodes 602 pictured in FIGS. 6A and 6B. A mixture of nano catalysts (e.g., a tri-nano recipe of nano Co, Ni and Sn) 806 may be adhered to the electrode 812/814/816 according to the teachings of U.S. Patent App. Pub. 2011/0114496 as discussed above. No separator is included between the electrodes 812/814/816 and thus separate cathodic and anodic chambers are not formed, which simplifies the design of the reaction vessel 800. Dimensions of the reaction vessel 200 may be varied to increase processing capabilities.

The monofunctional electrodes 812/814 can include a porous metal component 616 spot welded to one side of the substrate 614 and the bifunctional electrodes 816 can include porous metal components 616 spot welded to both sides of the substrate 614. FIG. 9 shows a top view of an example of a bifunctional electrode 816 with corrugated porous metal components 616 spot welded to both sides of the substrate 614. Referring back to FIG. 8, an electrical connection is made at the two monofunctional electrodes 812 and 814. Electrical contacts (not shown) are also provided for the two monofunctional electrodes 812 and 814. The electrodes 816 in the interior of the cells 802 receive their electrons from the ions involved in the electrochemical reactions. The electrodes 812/814/816 may be spaced apart to maximize efficiency of the system. For example, the space between the electrodes 812/814/816 may be in the range from about 0.75″ (19 mm) to about 0.063″ (1.59 mm), from about 0.375″ (9.53 mm) to about 0.063″ (1.59 mm), and from about 0.288″ (4.76 mm) to about 0.063″ (1.59 mm). Dimensions of the reaction vessel 600 may be varied to increase processing capabilities.

The example of FIG. 8 includes one reaction vessel 800 with one set of electrodes. In other embodiments, the reaction vessel 800 may include multiple sets of electrodes with each set arranged in series such that the electrolyte sequentially flows through each set of electrodes. The sets of electrodes include two monofunctional electrodes 812/814 and may include one or more bifunctional electrode(s) 816 between the monofunctional electrodes 812/814 as can be understood. In some implementations, a plurality of reaction vessels 800 may be connected in series, parallel, or a combination thereof such that the electrolyte flows through each reaction vessel 800.

During operation, electrolyte including the organic molecules may be passed through the reaction vessel via the inlet and outlet connections 804/806 and the electrodes 812/814/816 are energized to digest the organic molecules. During the cycle in which electrode 812 is negatively charged, hydrogen gas and hydroxyl ions are evolved from that electrode while consuming two water molecules and two electrons (2H₂O+2e⁻→2OH+H₂). That hydroxyl molecule diffuses to the first bifunctional plate 816 where that hydroxyl liberates its electron into the plate while creating a singlet oxygen (or nascent or atomic oxygen) and one water molecule (2OH⁻→½O₂H₂O+2e⁻). The electrons pass through the bifunctional plate 816 where it behaves as it did on the initial monofunctional plate 812, producing an H₂ and two hydroxyl ions. The process continues until reaching the last monofunctional plate 814 where the electrons exit to this positive plate. The polarity of the plates 812/814 is alternated when driven by a 100% duty cycle illustrated in FIG. 3B.

Referring next to FIG. 10 shown is an example of an electrochemical digestion system 1000. The electrochemical digestion system 1000 includes a reaction vessel 1002 with one or more cells such as, e.g., the reaction vessels of FIGS. 2, 5, and 8. The electrochemical digestion system 1000 can also include a pump 1004 or other means suitable for inducing flow of a fluid 1006 (e.g., an electrolyte solution including organic molecules) through the reaction vessel 1002. The electrochemical digestion system 1000 may be configured as a loop to allow recirculation of the fluid through the reaction vessel 1002 as depicted in FIG. 10 or may be a single pass system. Multiple reaction vessels 1002 may be grouped in series and/or parallel arrangements to optimize flow and current characteristics. For example, a plurality of reaction vessels 1002, each with one or more cells, may be connected in series to process the fluid 1006 in multiple stages. Mixing chambers may be included between the reaction vessels 1002 to allow for even distribution of the organic molecules between the cells of each reaction vessel 1002. In other configurations, reaction vessels 1002 may be connected for parallel processing of the fluid through multiple reaction vessels 1002. In one embodiment, among others, an electrochemical digestion system 1000 includes the four-cell reaction vessel of FIG. 8. The four cells 1002 were arranged in electrical series and parallel flow with both inlet and outlet manifolds 1008 and 1010 that are configured using three “Y” connectors on each side of the reaction vessel 1002. A power source 1012 supplies a voltage wave shape to the electrodes of the reaction vessel(s) 1002.

The fluid 1006 can be pumped using a small piston or other suitable pump 1004, which may be driven by, e.g., a DC motor 1014. The flow rate of the fluid 1006 may be adjusted to provide an optimum dwell time within the reaction chamber 1002 for digestion of the organic molecules. The fluid 1006 flows from a fluid reservoir 1016 through an inlet manifold 1008 into the cells of the reaction vessel 1002, before passing through the output manifold 1010 (which may comprise a reducing manifold) back to the fluid reservoir 1016. Adjustment of the flow rate of the fluid 1006 may be provided by adjusting the speed of the pump 1004 or by throttling the output of the pump 1004 using, e.g., a valve (not shown). In some implementations, turbulence may be induced at the outlet(s) of the reaction vessel 1002 to improve digestion of the organic molecules by the generated singlet oxygen that my still be present in the fluid 1006. In some cases, a discharge chamber may be included at the outlet(s) of the reaction vessel 1002 or the outlet of the outlet manifold 1010 to promote effective utilization of any singlet oxygen leaving the reaction vessel 1002. In other implementations, turbulence may be induced within the cells of the reaction vessel 1002 to aid in the breakdown of the organic molecules.

Ozone may be added to the fluid 1006 to enhance the electrochemistry and assist in the degradation of the organic molecules. The addition of air (or other gas) bubbles may also influence the reaction by saturating the fluid 1006 with non-reactive gases such as, e.g., nitrogen. The fluid flow rate through the reaction vessel 1002 may also be adjusted to improve or maximize efficiency. For example, a flow that is too high may hinder the reaction by limiting or reducing the time the electrolyte solution (or fluid) is adjacent to an electrode of the reaction vessel 1002. In some implementations, product of the digestion process is separated from the electrolyte solution (or fluid) by centrifuge and/or drying. In other implementations, the product may naturally separate from the electrolyte through buoyancy. The product may then be siphoned off the electrolyte before further processing.

Various experiments were performed using an embodiment of the electrochemical digestion system 1000 of FIG. 10. For example, a pump 1004 such as, e.g., a FLOWJET Model 2100-332 piston pump, which delivers about 0.33 liters/minute for each volt supplied to the DC motor, was used. The fluid reservoir 1016 may be, e.g., a three-necked beaker or other appropriate fluid container suitable for storing the electrolyte solution. Scale of the system 1000 may influence the type of fluid reservoir that is used. In one embodiment, the electrolyte solution 1006 was drawn out of a first neck of the beaker 1016 through a tube 1018 passing through a silicon stopper 1020. After passing through the reaction vessel 1002, the electrolyte solution 1006 is returned to the beaker 1016 through tube 1022, which passes through another silicon stopper 1020 in a second neck of the beaker 1016. In the example of FIG. 10, two tubes pass through another silicon stopper 1020 in the center neck of the beaker 1016. The first provides access for the addition of ozone through tube 1024 and aeration stone 1026. Ozone may be added to the electrolyte solution 1006 to enhance the electrochemistry and assist in the degradation of the organic molecules. The second is a sampling tube 1028, which may have a luger-lok connector for sampling using a syringe.

In each experiment, a total of 500 ml of electrolyte solution 1006 was circulated through the three necked beaker 1016 at about 5 liters/minute flow rate with the four cells of the reaction vessel 1002 electrically connected in series and the electrolyte flowing through an inlet manifold 1008 and outlet manifold 1010. Each cell of the reaction vessel 1002 contained a volume of about 28.5 cm³, so the total reaction chamber volume is about 74 cm³. The electrodes were coated with nano nickel, nano tin and nano cobalt according to the teachings of U.S. Patent App. Pub. 2011/0114496 as described above. The coated electrodes are very effective as water electrolysis electrodes when run in near eutectic KOH or NaOH electrolyte. The electrolyte solution 1006 used in the experiments included 1% organics (e.g., Starch or Cellulose) and 1% ion carrier (e.g., sodium chloride (NaCl), potassium hydroxide (KOH), or sodium hydroxide (NaOH)) in water depending on the particular experiment. Repeated circulation of the electrolyte solution 1006 through the reaction vessel 1002 during excitation of the electrodes by the power source 1012 breaks down the organic molecule chains (e.g., starch) in electrolyte solution 1006.

In a first example of the digestion process, an electrolyte solution 1006 including 1% KOH and 1% corn starch was utilized to study the effect on soluble organic molecules. The organic molecules in the electrolyte solution 1006 were digested using a corrugated coated expanded metal electrode for 24 hours, running at 340 mA (25 mA/cm²). The volume of electrolyte solution 1006 was 500 cc and the total electrode surface area was about 112 cm². The resulting fluid 1006, after processing through the reactive vessel 1002, was much clearer than the milky appearance of the starting fluid. Evaluation was performed using a colorimetric method using the well known iodine reaction with starch, which produces a deep blue color. Using a spectrophotometer, the colorimetric method was developed, which proved to be reliably quantitative. First, a series of absorption readings were taken, at one low starch concentration, to find the maximum absorption for that blue color. The wavelength was shown to be 620 nm for the iodine-starch complex. Then a series of starch concentrations were run at that wavelength giving a calibration curve. It was recognized that the iodine is actually staining only the amylose portion of starch (about 15%), not the amylopectin (about 85%), but a loss of one strongly suggests that both are being digested.

Samples of the fluid 1006 were drawn frequently during the digestion process and during subsequent digestion experiments using potato starch. The results are given in TABLE 1. The rates shown are the slope at the beginning of digestion, since it finds an asymptote as the supply of starch is lost to digestion.

TABLE 1 Compared to mg/hr mg/AHr mg/WHr thermal Corn Starch 316 1859 895 36 Corn St @75 C. 413 2430 1364 55 Potato Starch 536 3037 1564 63

In a second example of the digestion process, an electrolyte solution 1006 including 1% KOH and 1% wood flour such as, e.g., pine flour, oak flour and micro crystalline cellulose (MCC) was used to study the effect on insoluble organic molecules. The electrolyte solution 1006 including 1% Pine Flour in 1% KOH was digested using a corrugated coated expanded metal electrode running at 340 mA (25 mA/cm²) for 24 hours. The volume of the electrolyte solution 1006 was 500 cc and the total electrode surface area is about 112 cm². The resulting material appearance was very different from the original appearance with all color being removed and a much lower volume of settled matter.

The samples were vigorously mixed, and 50 milliliters were passed through dried and weighed filter paper in a 55 mm Buchner funnel. The resulting filtrate was collected in a clean, dry and pre-weighed filtration beaker, and 20 milliliter of this was transferred to a ceramic weighing vessel. Both the filter paper and the vessel were then transferred to a 105 degrees Celsius (° C.) drying oven for about 16 hours. All materials had been pre-dried and weighed, so the weights reflected the new weight added from the insoluble material (on the filter papers) and the soluble materials (in the solution). The results are shown in TABLE 2.

TABLE 2 Compared mg/hr mg/AHr mg/WHr to thermal Oak Flour 5 30 265 11 Pine Flour 17 100 905 36 MCC 5.9 35 299 12

A common method to break down organic molecules is to heat the solution to 350° C. at which temperature the molecules spontaneously break down. The energy it takes to heat 500 cc of water from 21 to 350° C. is 688 BTU or 202 Wh. In the 24 hours under electrochemical digestion, essentially all of the starch (1% of 500=5 grams=5000 mg) is consumed. To thermally break down that amount of organic material, the rate is 25 mg/WHr is calculated. The last column in Tables 1 and 2 show the ratio of the power efficiency improvement using the electrochemical method to break down organic molecules.

Other organic molecules such as, but not limited to, cellulose, hemicellulose, lignin, lignite coal slurry, algae (e.g., for lipid extraction), viruses and bacterium for decontamination, wastewater, etc. may be digested using the disclosed system and method. For example, cellulose concentrations in the range from about 0.1% to about 20%, from about 0.5% to about 10%, and from about 0.75% to about 2.5%, may be digested. The concentration of organic molecules may be based upon the viscosity of the electrolyte.

Heating can improve the digestion of the organic molecules in the fluid. The digestive processes, such as those in a continuous flow reaction vessel using fluid that is heated directly, can be enhanced by using heat-producing electrode elements that are coated with nano catalysts such as those previously described. When properly formulated, the catalytic surface can enhance the electrolysis of water on the heat-producing electrodes, making them electrochemically active. Water electrolysis occurring at the plates produces singlet oxygen's during the heating process. The neutral singlet oxygen atoms react with oxygen atoms within the organic molecules resident in the fluid, thereby liberating diatomic oxygen and reducing the overall oxygen content of the organic material. This reduction in oxygen content increases the energy density of the resulting organic. It also would increase the liberation of buoyant lipids through the lysing of cell walls and vacuoles. The hydrogen produced may well hydrogenate the lipids on the catalytic surface, thus increasing their energy content.

The present disclosure discusses controlled heating and electrochemical degradation of electrically conductive fluids e.g. gases, pastes, suspensions, plasmas, slurries and liquids, as we let such a fluid flow (or rest) in a pipe/reservoir/chamber/reactor, or similar vessel. As discussed herein, the term pipe may be used interchangeably with any of the terms discussed above as the particular device/embodiment requires. A multi-frequency (MF) heating concept may be applied to power one or more elements of the system that are electrically insulated from other elements of the system. The applied power can be direct current (DC) or alternating current (AC) and/or electromagnetic frequencies making use of any and all frequencies that are permitted and available including, but not limited to, those in the RF range. Various elements that are part of the insulating system or added as part of the internal components may provide direct and indirect heating of the fluid contained in the system. Insulators, seals, and mechanical supports may be required to hold the device together and in alignment under high fluid pressure. Dimensional changes in materials caused by increasing or decreasing temperatures can be accounted for in the design of the system.

A power source causes electric current to flow through the fluid and heat it to high temperatures. Heating can occur by the direct interaction of applied electric fields with the fluid. The frequency may be selected based upon, e.g., the conductivity and/or dielectric property of the fluid and/or the effect on digestion of the organic molecules. The desired power for the source can depend on, e.g., the diameter of the pipe, shape and dimensions of the electric conductors and insulators, and the dielectric properties of the fluid, as well as other factors. The power required for the source may also depend on the specific heat of the fluid, its flow rate, the thermal insulation used around the pipes and the desired temperature of the fluid.

FIG. 11 is a cross-sectional drawing illustrating an example of a heating system 1100 that is installed collinear with a pipe (not shown) to heat fluid 1102 flowing through the pipe. The heating system 1100 is connected to the pipe by means of two flanges 1104. The fluid 1102 to be heated flows through two outer pipe sections 1106 a and 1106 b, an inner pipe section 1108 and two electric insulators 1110, which separate the inner and outer pipe sections. Seals 1112 between the insulators 1110 and the pipe sections 1106/1108 prevent leakage of enclosed fluid 1102. Note that the raw fluid (i.e., pretreated and/or preheated) can be referred to herein as feedstock and the post treatment fluid can be referred to as product. The diameter and wall thickness of the pipe sections 1106/1108 are chosen to match the dimensions and operating conditions of the fluid system to which the heating system 1100 is connected. Mechanical supports (not shown) may be used to hold the heating system 1100 together during operation under high fluid pressures and to accommodate dimensional changes caused by changing temperatures.

The electric insulators 1110 electrically isolate the inner pipe section 1108 from the adjacent outer pipe sections 1106 a and 1106 b. The material used for electric insulators 1110 can be chosen to withstand the temperatures and pressures of fluid 1102 being heated. Such materials include, but are not limited to, high temperature polymers and ceramics. The length of the electric insulators 1110 may be adjusted to alter the heating pattern over the cross section of pipe sections 1106/1108. Shorter insulators 1110 cause greater heating near the walls of the pipe outer pipe sections 1106 a and 1106 b and longer insulators 1110 cause the heating to extend more towards the center of the pipe outer pipe sections 1106 a and 1106 b to provide more uniform heating of fluid 1102.

The seals 1112 can be made of ceramics, high temperature polymers or high temperature polymer composites incorporating inorganic fibers to add strength, as well as other materials, and are chosen so that they may not be easily corroded by fluid 1102. The seals 1112 can be any shape, such as washer-shaped or toroidal-shaped, appropriate for the configuration of the heating system 1100. They can be at the ends of insulators 1110, on the outer surface of insulators 1110 or on the inner surface of insulators 1110 depending on whether the insulators 1110 are in line with the pipe sections 1106/1108, inside the pipe sections 1106/1108, or outside the pipe sections 1106/1108.

An electrical power source 1114 may be connected between the inner pipe section 1108 and the two outer pipe sections 1106 a and 1106 b. In FIG. 11, the outer pipe sections 1106 a and 1106 b are connected to a building ground 1116, which also grounds the flanges 1104. An electric shield 1118 may be electrically connected to and surrounds flanges 1104. The shield 1118 can be included for safety reasons as well as to limit radiation from the electric power source 1114, which may cause electrical interference to other electronic equipment. A thermocouple 1120 can be located at the downstream end to monitor the temperature of the fluid 1102. The output of the thermocouple 1120 is connected to a controller 1122 to control the output of electrical power source 1114 to maintain the desired temperature.

To aid in the following description, five regions are defined for later reference. Region 50R is before the upstream insulator 1110 a. Region 60R is at upstream insulator 1110 a. Region 70R is between the upstream insulator 1110 a and the downstream insulator 1110 b. Region 80R is at the downstream insulator 1110 b. Region 90R is after the downstream insulator 1110 b. The electric power source 1114 causes electric current to flow through the fluid 1102 between regions 50R and 70R and also between regions 70R and 90R. This electric current heats fluid 1102 directly because of the fluid's electrical conductivity or equivalently its dielectric loss properties. The specifications for electric power source 1114 depend upon the type of fluid 1102 being heated, its flow rate and the temperature to which it is to be heated as well as other factors. For highly conductive fluids 1102, such as salt water, a low frequency alternating current source can be used. Less conductive fluids can use higher frequency alternating current sources. A number of commercial power sources are available that can be used.

The optimum frequency depends on various factors including, but not limited to, the dielectric properties of the fluid 1102. The optimum voltage for electric power source 1114 can depend on, e.g., the diameter of the pipe sections 1106/1108, length of electric insulators 1110 as well as the dielectric properties of fluid 1102. The power required for electric power source 1114 depends on the specific heat of fluid 1102, its flow rate, the thermal insulation used around the heating system 1100, and the desired fluid 1102 temperatures. The power needs for the digestion of the organic molecules may also be considered when evaluating capabilities of the electric power source 1114. If the power required exceeds the power levels of any single commercially available electric source, two or more heating systems 1100 and their associated electric power sources can be installed along the pipe to achieve the required power level.

Thermocouple 1120 allows measurement of the fluid's temperature immediately after it has been heated. The temperature of the fluid 1102 may be kept at the desired value by using this measured temperature to control the power level of electric source 1114 using, e.g., a standard commercially-available controller 1122.

The electric current flow pattern is now discussed. When insulators 1110 are short, the current flow occurs mostly close to the pipe walls in regions 60R and 80R and only a short distance upstream and downstream of these regions. This results in the greatest heating occurring near the pipe walls close to insulators 1110. For turbulent fluid flows, mixing occurs, which produces a more uniform heating of the fluid 1102. For laminar flow, where the fluid flow is slow at the walls of the pipe sections 1106/1108 and rapid near the center of the pipe sections 1106/1108. Because little or no mixing occurs, the fluid 1102 may become overheated at the pipe wall. This overheating at the pipe wall can be reduced by increasing the length of insulators 1110 to cause the electric current flow to move more towards the center of the pipe sections 1106/1108. However, because of the velocity profile for laminar flow of the fluid 1102, the heating can still be excessive at the pipe wall.

A number of different current distribution parts may be added to the heating system 1100 to produce a more uniform heating of the fluid 1102 by improving the electric current flow pattern and by physically mixing of the fluid 1102 before, during and/or after it is heated, as will be described. Referring to FIG. 12, shown are examples of various basic current distribution parts that can be used in various implementation of the heating system 1100 (FIG. 11) to alter the electric current flow pattern to bring more electric current flow to the center of the pipe and/or to cause mixing of fluid 1102 (FIG. 11) to promote more uniform heating. These basic current distribution parts may be fastened inside the pipe sections 1106/1108 by welding or other appropriate fastening means.

A first current distribution part 1202 includes two flat metal plates intersecting at right angles about their center lines. The size of the part may be such that it may snuggly fit into pipe sections 1106/1108 (FIG. 11) and can be held in place by welds or other means although the size, configuration, and positioning of the parts may be varied to other arrangements. This current distribution part 1202 can be modified by making the front and/or rear ends different shapes, such as, for example, sharp points, blunt points, or rounded curves for the purpose of altering the electric field pattern. Other current distribution parts similar to current distribution part 1202 may include three or more intersection plates, which can also be used to improve the electric current pattern. The length, placement and angular orientation of the current distribution part 1202 along sections 1106/1108 may be chosen to provide the best uniformity of heating.

A second current distribution part 1204 may include two intersecting flat metal plates that have been deformed so that their outer edges form four helices. The helices shown in FIG. 12 have an 80 degree right hand twist, but greater and lesser degrees of twist can be used. Right and left handed helices can be used. As in current distribution part 1202 the front and rear ends can have a variety of different shapes, such as points or smooth curves. The height, width, length, placement and orientation of current distribution part 1204 along pipe sections 1106/1108 (FIG. 11) may be chosen to provide the best uniformity of heating and fluid mixing. When the part stands alone with no other support, its height and width may be such that it fills the interior of pipe sections 1106/1108 and is held in place by welds or other means. Current distribution part 1204 has the same electrical function as current distribution part 1202, but it also promotes physical mixing of the heated fluid 1102 (FIG. 11) to provide more uniform heating. In other embodiments, current distribution part 1204 can have more than two intersecting plates, such as three, four or more.

A third current distribution part 1206 includes a plurality of parallel metal plates. In FIG. 12, seven plates are shown, but other quantities of plates can be used. The planes of the plates are parallel to the axis of pipe sections 1106/1108 (FIG. 11) so the fluid's flow is not disturbed. This basic current distribution part 1206 can be modified by making the front and/or rear ends different shapes, such as sharp points, blunt points, or rounded curves for the purpose of altering the electric field pattern. The length, placement and orientation of current distribution part 1206 along pipes section 1106/1108 may be chosen to provide the best uniformity of heating.

Another current distribution part 1208 is similar to part 1206 except that the metal plates are not parallel to the axis of pipe sections 1106/1108. The reason for their not being parallel to the axis of pipe sections 1106/1108 is to alter the direction of the fluid flow to cause physical mixing of fluid 1102 (FIG. 11) and thereby improve uniformity of heating. The sketch of the current distribution part 1208 shown in FIG. 12 shows all plates parallel to one another, but this need not be the case. The plates can also be curved to promote mixing. This basic current distribution part 1208 can be modified by making the front and/or rear ends different shapes, such as sharp points, blunt points, or rounded curves for the purpose of altering the electric field pattern. The plates can be of different lengths along pipe sections 1106/1108 and different angles to the axis of pipe sections 1106/1108 to increase physical mixing. The length, placement and orientation of current distribution part 1208 along pipe sections 1106/1108 can be chosen to provide the best uniformity of heating and fluid mixing. Current distribution part 1210 is similar to current distribution parts 1206 and 1208, except that it incorporates intersecting metal plates.

Other current distribution parts 1212 a and 1212 b may be described as auger-shaped metal disks. Current distribution part 1212 a is right handed and current distribution part 1212 b is left handed. The pitch of the auger can be selected for best physical mixing of fluid 1102 (FIG. 11). In addition to providing mixing, current distribution parts 1212 a and 1212 b may function to bring the electric current flow from the walls of pipe sections 1106/1108 (FIG. 11) to the center of pipe sections 1106/1108. The diameter, pitch, handedness placement and orientation of current distribution parts 1212 a and 1212 b along pipe sections 1106/1108 may be chosen to provide the best uniformity of heating and fluid mixing. When current distribution parts 1212 stand alone with no other support, their diameters may be chosen to fill the interior of pipe sections 1106/1108 so that they can be held in place by welds or other means.

Current distribution part 1214 is a metal cylinder that could be placed along the axis, or other location, of pipe sections 1106/1108 and held in place in a variety of means. In some embodiments, the cylinder of current distribution part 1214 may be combined with one of the above-mentioned parts by welding or other means. For example, the cylinder could be combined with either current distribution part 1202 or 1204 with the cylinder axis along the intersection of the metal plates forming parts 1202 or 1204. The cylinder may also be combined with one or more of the auger-shaped current distribution parts 1212. In these embodiments, the cylinder could run through the center of one or more of the current distribution parts 1212. The ends of the cylinder of current distribution part 1214 can be of any suitable configuration and geometry including, but not limited to, flat, pointed or curved. Its purpose is to improve uniformity of heating as well as promote physical mixing of fluid 1102 (FIG. 11).

Other current distribution parts 1216 may be shaped as a frustum of a conical cone. As with current distribution part 1214, current distribution part 1216 may be held in place by combining it with other current distribution parts. The ends of current distribution part 1216 can be of any suitable configuration and geometry including, but not limited to, flat, pointed or curved. Its purpose is to improve uniformity of heating as well as promote physical mixing of fluid 1102.

FIG. 13 are graphical representations illustrating examples of configurations of several current distribution part of FIG. 12 that may be placed in heating system 1100 shown in FIG. 11. In a first example, three current distribution parts 1302 a, 1302 b and 1302 c (based on current distribution part 1202 of FIG. 12) are shown at the top of FIG. 13. As stated above, current distribution part 1202 can be modified by making the front and/or rear ends different shapes, as shown in FIG. 13. For current distribution parts 1302 a and 1302 c, corners have been removed on one end. For current distribution part 1302 b, corners have been removed on both ends. Current distribution part 1302 a may be placed in region 50R of FIG. 11, current distribution part 1302 b may be placed in region 70R of FIG. 11 and current distribution part 1302 c may be placed in region 90R of FIG. 11.

At the bottom of FIG. 13 are shown three current distribution parts 1312 a, 1312 b and 1312 c, which are based on a combination of current distribution parts 1212 a and 1212 b. Current distribution part 1312 a may be made of both current distribution parts 1212 a and 1212 b and may be placed in region 50R. Likewise, current distribution part 1312 b may be made of both current distribution parts 1212 a and 1212 b and may be placed in region 70R. Current distribution part 1312 c may be made of both current distribution parts 1212 a and 1212 b and may be placed in region 90R. While not shown for current distribution parts 1212 a and 1212 b, in some embodiments the current distribution parts 1212 may be used in combination with current distribution part 1214, which could run through the center of the parts to add support and stability.

Shown in the middle of FIG. 13 are three current distribution parts 1306 a, 1306 b and 1306 c, which are based on current distribution basic part 1206 of FIG. 12. Current distribution part 1306 a may be placed in region 50R, current distribution part 1306 b may be placed in region 70R and current distribution part 1306 c may be placed in region 90R. FIG. 14 illustrates the placement of the three current distribution parts 1306 a, 1306 b and 1306 c in the heating system of 1100 of FIG. 11. FIGS. 15 and 16 show examples other configurations of current distribution parts within a heating system. Other combinations and placement of various current distribution parts of FIG. 12 may also be implemented as can be understood.

Referring to FIG. 14, shown is the placement of the three current distribution parts 1306 a, 1306 b and 1306 c in the heating system 1100 of FIG. 11. Other current distribution parts such as, e.g., the current distribution parts illustrated in FIG. 12, may be positioned with the heating system 1100 as shown in FIG. 14. The current distribution parts 1306 a, 1306 b and 1306 c have been be modified for the example of FIG. 14. The purpose of current distribution parts 1306 a, 1306 b and 1306 c is to cause the electric current flow that normally flows across insulators 1112 in regions 60R and 80R close to the pipe wall, to be moved nearer to the center of the pipe so the heating is more uniform. The electric current flow pattern can be altered, e.g., by changing the angle and size of the corners removed by rounding the resulting angular corners; by rotating the electrodes so that the plates in neighboring current distribution parts do not lie in the same plane, and/or by other modifications. The electric current flow pattern can be further altered by changing the number of plates, having an unequal number of plates in adjacent current distribution parts 1306 a, 1306 b and 1306 c and/or by changing the distance between adjacent current distribution parts 1306 a, 1306 b and 1306 c. Current distribution part 1306 a may be electrically connected to outer pipe section 1106 a in region 50R, current distribution part 1306 b may be electrically connected to inner pipe section 1108 in region 70R and part 1306 c may be electrically connected to outer pipe section 1106 b in region 90R.

FIG. 15 shows another example of heating system 1100 including current distribution parts (which may be comprised of any suitable materials including, but not limited to, metal) such as a combination including, e.g., current distribution parts 1202 and 1214 of FIG. 12, which are labeled 1302 b and 1514, respectively. Current distribution part 1302 b includes a plurality of intersecting plates. Current distribution part 1302 b supports cylindrical current distribution part 1514 with the axis of the cylinder along the center line of pipe sections 1106/1108. In other embodiments, other current distribution parts such as, e.g., part 1206 of FIG. 12 including parallel plates that support cylindrical part 1514. Cylindrical current distribution part 1514 has rounded ends, but they could be other shapes (e.g., bulbous) to alter the flow of fluid 1102 or increase current flow to the center of the pipe sections 1106/1108. The combined current distribution parts 1302 b and 1514 are electrically connected to inner pipe section 1108 in region 70R. Cylindrical current distribution part 1514 extends upstream through region 60R into region 50R and downstream through region 80R into region 90R. Thus, the electric current paths that normally flow close to the pipe walls near regions 60R and 80R are brought into the center of outer pipe section 1106 a in upstream region 50R as well as into the center of outer pipe section 1106 b in downstream region 90R. The diameter and length of cylindrical current distribution part 1514 can be chosen to achieve uniform heating of the fluid 1102 in laminar flow by concentrating the current paths near the axis of the pipe where the flow is normally largest for laminar flow. The presence of the cylinder at the center of the pipe also slows the flow at the axis of the pipe to further achieve uniform heating over the entire cross section of pipe sections 1106/1108.

FIG. 16 shows an example of a heating system 1600 that may be an expanded version of the heating system 1100 of FIGS. 14 and 15. It may comprise two heating systems separated by a pipe section 1606. Cylindrical current distribution part 1614 runs through the axial length of pipe section 1606. The interior of pipe section 1606 constitutes region 90R of the upstream device and constitutes region 50R of the downstream device, so it is labeled region 90/50R. As in heating system 1100, electric current flow occurs between the walls of pipe sections 1106 a/1106 b and cylindrical current distribution part 1614 in regions 50R and 90R. In heating system 1600, additional currents flow between the walls of pipe section 1606 and cylindrical current distribution part 1614 in region 90/50R. Pipe section 1606 can be made very long to increase the length over which heating occurs. Heating system 1600 may be useful for fluids 1102 that have small electrical conductivity because the long region 50/90R over which electric current flows may reduce the electrical resistance presented to electric power source 1114 so that lower voltages can be used to deliver the required amount of power. To accommodate differential thermal expansion that may occur, either current distribution part 1302 a or 1302 b may be free to slide along the pipe walls. For example, a current distribution part may be secured at a fixed point or the current distribution part may be designed to accommodate the thermal expansion of the materials.

A continuously circulating heating system can be constructed including a coaxial electromagnetic heating apparatus (or heating element) to efficiently heat a fluid contained in a pipe and/or piping system. The system may operate with or without a circulating pump. For example, the fluid may be circulated without a circulating pump by using thermal density gradients. A vertical system circuit orientation can be used to heat a fluid to super critical temperatures yet safely and efficiently contain the fluids at the increased temperatures and pressures. The basic principle of operation is based on the change in density of fluids with temperature, i.e., the fluid density decreasing when it is heated and the fluid density increasing as it cools.

FIG. 17 illustrates an example of continuous feed through a system 1700 with heated reaction vessel 1702, a power source 1704, and electrode(s) 1706 such that fluid may flow continuously, though not circulating. The continuously circulating system 1700 of FIG. 17 also includes sampling valves 1708, a pressure relief valve 1710, reservoir and ballast 1712, and sample fill valve 1714. The equipment can additionally include an expansion tank to compensate for the effect caused by the fluid density decrease as the temperature rises toward the supercritical condition. The incompressibility of water at all densities means that an expansion chamber (e.g., reservoir 1712) is used to prevent system rupture of the apparatus. In addition, a pressure vent (e.g., pressure relief valve 1710) may be included as a safety device to allow excess pressure to be safely released. It may further be advantageous to include one or more temperature and/or pressure gauges along the flow path as well as a sampling system.

In the example of FIG. 17, the electrical connection from the power source 1704 to the electrode(s) 1706 may pass through a ceramic tube insulator. In addition, a ground connection may be made to the stainless steel circulating system. The electrode(s) 1706 may be supported on the ceramic tube that carries the electrical wire to the electrode(s) 1706. At the top of the expansion tank 1712 is a fill valve 1714 that may be used to add fluids to the heated reaction vessel 1702. In some embodiments, the power source 1704 (e.g., an RF generator) can be attached with the positive connection made to the electrode 1706, which is electrically isolated from ground by the ceramic tube, and the ground attachment may be made to the reaction vessel 1702.

In the embodiment of FIG. 17, there is no need for a circulating pump because the system is gravity driven based on the density gradients. In some implementations, algae circulated through the system 1700 under the influence of one or more RF generators produced matter in solid form, liquid form and gaseous form. In some embodiments, the fluid (e.g., algae and water mixtures) may be heated to supercritical conditions wherein the algae can degrade to methylene chloride and other water soluble products. In some implementations, various algae slurries were heated to supercritical or near supercritical temperatures and the algae slurries were degraded. Further tests were conducted on the products produced including testing by HPLC, GC, and GC-mass spectrometry.

As discussed above, various embodiments may include one or more pumps to aid in circulating the fluid(s). Such pumps may be present in various locations along the flow path. Such pumps can increase flow rates over embodiments without circulating pumps. In some embodiments, additional reservoirs may be included in the system to accommodate the influence of the circulating pumps.

A flow through heating system can be constructed including a coaxial heating apparatus (or heating element) to efficiently heat a fluid that continuously flows through a pipe and/or piping system. Referring to FIG. 18, shown is an example of a flow through system 1800 that is modular with one (or more) heating element(s). The flow through system 1800 of FIG. 18 can be designed to operate at power levels up to 15 KW, though other embodiments may have higher or lower power levels. Illustrated is an exemplary continuous flow system 1800 with a heated reaction vessel 1802 including a chamber 1804 containing electrode 1806, which is held in position by spacers 1814 and spacer legs 1816. A conductor 1812 supplied power to the electrode 1806 through ceramic insulator 1808 passing and fittings 1810.

The design illustrated in FIG. 18 utilizes Swagelok stainless steel (SS) seals and features Techlok sealing flanges. The flow through system 1800 may utilize ceramic electrical insulators 1814 and ceramic spacers 1816 to maintain the position of the electrode 1806. The flow through system 1800 may also have a back flush feature to allow for clearing of any plugging or needed cleaning which is a convenient feature for high production volumes. The heating element (electrode 1806) is designed with high strength corrosion resistant alloys and located in the center of the process fluid flow. This configuration does not rely on heat transfer through the thick walls that may be needed to contain the high pressure that exists under the processing conditions and makes it possible to completely and separately control the heating of each electrode 1806. Further, its modular design allows replications of the basic flow through system 1800 to provide scalability to generate any desired throughput at production rates, while allowing in-line maintenance or replacement of heating elements or power generators without system shutdown.

Although the flow through system 1800 of FIG. 18 uses a ceramic tube to provide electrical insulation of the electrode 1806, other embodiments may use other electrical pass-through technology and/or feature a corrosion resistant alloy as a protective shroud around the ceramic electrical insulator. This configuration may eliminate pressure and other physical damage problems which could develop and will need only one metal-to-metal seal for the electrical connection and metal. The other seals may be Techlok sealing flanges, or other suitable flanges. Copper gaskets may be used to connect the electrode 1806 to the reaction vessel 1802. The illustrated system 1800 may also use various pipe sizes and appropriate flanges. The outside of the system 1800 may use electric resistance heat tracing and be covered with a high temperature insulation material around the heating elements and other components.

As noted above, the heated flow through system 1800 can be replicated based on the production rate sought and the capacity of the power supplied to the systems 1800. The flow through system 1800 illustrated in FIG. 18 may be approximately 3 feet long with Techlok flanges are used to connect the units. Each flow through system 1800 can have its own power supply to provide redundancy and control during operations. In some implementations, the ceramic insulator 1808 may be clad with stainless steel. Some embodiments of the insulator may also have graded seals between the stainless steel cladding and the ceramic insulator and between the ceramic insulator and the copper conductor. The power pass-through may be connected with Techlok flanges to the heating element. This exemplary unit is designed to contain 5000 psi at 400° C.

FIG. 19 illustrates a schematic view of an example of a coaxial electrode applicator 1900 which is electrically insulated from the piping system, placed in the center of the pipe, and connected to the “hot” side of power source (e.g., an MF generator). Illustrated are a pipe wall 1902, an electrode 1904, conductor to power 1906, and fluid flow 1908. The continuous flow system 1800 is electrically insulated with the coaxial electrode is attached to ground.

Various embodiments may employ one or more coaxial applicators. Each applicator can include two electrodes with the electric current passing from one electrode to the other electrode directly heating the fluid between them. In the example of FIG. 19, a first electrode is the wall 1902 of the pipe that conveys the fluid 1908 to be heated. The other electrode is the cylindrical current distribution part 1904 that lies on the central axis. For example, the design dimensions of one embodiment, among others, may be a length of L=24,″ pipe radius of R=2,″ an electrode radius of r=0.5″ for 13.56 MHz RF input power and r=1.25″ for 60 Hz AC input power.

The inner radius (R) of the pipe, the radius (r) of the of the central coaxial electrode, and the length (L), along with the electrical properties of the fluid 1908 determine the electrical impedance of the flow through heating system 1900, which must be within certain ranges to obtain good coupling of power from the RF generator or AC power line to the electrode 1904. Electrical matching networks for RF can provide some compensation, but by careful design using optimum dimensions, efficient coupling of power can be achieved. Optimum dimensions vary with frequency and thus are different for 13.56 MHz RF and 60 Hz AC power input.

Digestion of organic molecules can be improved by including a catalytic coating to the current distribution parts of FIGS. 12-16. The additional surface area adds to the effectiveness of the catalytic coating applied to these surfaces. These catalytic coatings may be applied as described in “Electrochemical Devices, Systems and Methods” (U.S. Patent App. Pub. 2011/0114496, published May 19, 2011, and PCT Pub. WO 2010/009058, published Jan. 21, 2010), both of which are hereby incorporated by reference in their entirety. Embodiments of high-surface area catalytic coated electrodes can include three-components:

-   -   A first component may be, substantially, a substrate such as a         plate or other structure having a regular or complex geometry         and having a smooth or rough surface and consisting of         transition metals including among others, nickel, iron,         stainless steel, or silver. The first component may be defined         by a reticular structure, a plate, a random textile, channeled,         dendritic, foam, or self-similar patterned or unpatterned         structure with internal channels or external grooves or pits,         spines, fins, or any kind of structure that permit fluids or         fluid components to reach a surface or surfaces thereof,         including a surface of a material layered on the substrate,         either by convection, advection or diffusion.     -   A second component may be, substantially, a component of         transition metals including among others, nickel, gold or silver         attached to the first component, for example by electroplating.     -   A third component may be, substantially, metal particles;         preferably nano-sized metal particles and/or mixed nano-micron         sized particles of transition metals including among others         iron, tin, nickel, silver, manganese, cobalt and alloys and         oxides of these metals.     -   The third component may be partially embedded in the second         component and may be principally of nano and/or micron sized         particles partially embedded in the second component but exposed         such that when the completed electrode is immersed in         electrolyte, the third component is in intimate contact with the         electrolyte. The third component may be partially covered by the         second component but, due to the second component's overlying         the third component closely, so conforming to the third         component size and shape that the third component imparts a         roughness to the surface of the second component that is         responsive to the size and shape of the third component.         Nano catalysts may also be coated onto a porous current         collector, as described with respect to FIGS. 6A, 6B and/or 9,         and then tack welded to the current distribution parts such as         the examples shown in FIG. 12.

Referring now to FIG. 20, shown are cross sectional views of heating plates of current distribution parts including nano catalysts. The nano catalysts 2002 may be applied as described by PCT Pub. WO 2010/009058 or other methods that leave the catalytic powders exposed to the liquid boundary layer, but also result in very little electrical resistance between the current collecting base metal of the plates 2004 and the nano catalytic powders. For example, the nano catalysts 2002 may be applied directly to a plate 2004 a of a current distribution part or to a porous metal component (e.g., nickel foam) 2006 a including the nano catalysts 2003 may be attached to a plate 2004 b. In some implementations, the porous metal component 2006 b may be shaped to increase the exposure of the catalysts before being attached to the plate 2004 c.

As power is applied to the plates 2004 for resistive heating, electrolysis will occur on the plates. As previously described, the electrolysis will produce singlet oxygen atoms, which are very reactive and will attack the organic molecules in the surrounding fluid. The nano catalysts 2002 can enhance the electrolysis on the heat-producing plates 2004 of the current distribution parts, making them electrochemically active. The likely target is oxygen molecules within the organic molecules, forming diatomic oxygen, which then bubbles off by buoyancy. An example of such an organic molecule is shown in FIG. 1 where the inter-glucose oxygen reacts with the singlet oxygen, breaking the glucose chain. The singlet oxygen may also break proteins, releasing lipids held in vacuoles within cells such as, e.g., algae or kelp. The result is a lowered oxygen content of the remaining solids, which thus increases the energy density (i.e.: BTU's per pound) of those solids.

The nano catalysts can be included in the heating systems of FIGS. 14-19 to improve digestion of organic molecules in the fluid flowing through the systems. In some implementations, the catalysts for electrolysis may be located in a pre-heating section of a digester to free lipids, which would then be more efficiently transformed into more useful forms by the thermal process.

Referring next to FIGS. 21A-21C, shown are views of an example of concentric tubes 2100 that may be used as current distribution parts in a heated reaction vessel. FIG. 21A shows the cross-section along the longitudinal axis of the concentric tubes 2100. In the example of FIGS. 21A and 21B, the outer tube 2102 and the inner tube 2104 comprise two monopolar powered electrodes with nano catalyst on one side of the tube. In some implementations, the outer tube 2102 may be the wall of a pipe section such as 1106 or 1108 of FIG. 11. In the embodiment of FIG. 21, there are two intermediate tubes 2106 and 2108 including bipolar electrodes with nano catalysts on both sides of the tubes. In other implementations, one, three, or more intermediate tubes including a bipolar electrode may be used. In some cases, an intermediate tube may not be included. Insulating manifold components 2110 on both ends of the concentric tubes 2100 positions and supports the tubes 2102-2108. Power is supplied to the outer tube 2102 and the inner tube 2104. The electrical contacts to the inner tube 2104 and the outer tube 2102 are not shown in FIG. 21A. In one example, power may be provided to the inner tube 2104 in a fashion similar to that described with respect to FIGS. 18 and 19. A wave form at a frequency above DC may be applied as discussed above. The voltage wave shape may be applied in a range of about 100 Hz or lower, a range of about 10 Hz or lower, a range of about 1 Hz or lower, a range of about 0.1 Hz or lower, a range of about 10 mHz or lower, a range of about 1 mHz or lower, or a range of about 0.1 mHz or lower. The bipolar electrodes of the intermediate tubes 2106 and 2108 gain their electrical and electrochemical activity from ionic transport of the electrons.

FIG. 21B shows a cross-sectional view of the concentric tubes 2100 perpendicular to the longitudinal axis as indicated by C-D line 2112 of FIG. 21A. The constant spacing between adjacent tubes is maintained by the insulating manifold components 2110. FIG. 21C shows a cross-sectional view of the insulating manifold component 2110 perpendicular to the longitudinal axis as indicated by A-B line 2114 of FIG. 21A. The material of the insulating manifold components 2110 are chosen to withstand the operating conditions of the heated reaction vessel such as, e.g., temperatures above 300° C., while maintaining their insulation and strength capabilities. Examples of materials include, e.g., a phenolic like Bakelite and/or Noryl, among others. A shock-absorbing gasket (not shown) may be inserted between the concentric tubes 2100 and the insulating manifold components 2110. The gasket may be, e.g., unsintered PTFE or other appropriate material.

FIG. 22 shows enlarged views of portions of a monopolar electrode of the outer and inner tubes 2102 and 2104 (FIG. 21) and a bipolar electrode of the intermediate tubes 2106 and 2108 (FIG. 21). The tubes 2102-2108 include a supportive portion 2202 of metal or alloy (e.g., a stainless steel such as SS304 or SS316) or other low corrosion structural alloys. As in FIG. 20, the catalytic coating may be directly coated on one or both sides of the supportive portion 2202 of the tube 2102-2108 or applied to a porous substrate (e.g., a foam or expanded nickel) which is affixed to the supportive portion 2203 using, e.g., spot-welding. In the examples of FIG. 22, porous substrates 2204 including nano catalysts are affixed to the sides of the concentric tubes 2100 as appropriate. The outer and inner tubes 2102 and 2104 have the coating only on the side that participates in the chemical reaction while the intermediate tubes 2106 and 2108 are coated on both sides.

Referring now to FIGS. 23A-23E, shown views of an example of interleaved current distribution parts 2300 in a heated reaction vessel. In the example of FIGS. 23A-23E, the current distribution parts 2300 includes a variation of the combination of current distribution parts 1202 and 1214 of FIG. 12 as well as fins (or plates) extending toward the center of the heated reaction vessel. FIG. 23A shows a cross-sectional view perpendicular to the longitudinal axis of the interleaved current distribution parts 2300. For example, wall 2302 may correspond to the inner pipe section 1108 of FIG. 11. Eight fins 2304 extend inward from wall 2302 toward the central axis. A current distribution part aligned with the central axis includes eight fins 2306 that extend radially outward from a tube or rod 2308. The fins 2304 extending inward from wall 2302 are interleaved with the fins 2306 that extend radially outward from the tube or rod 2308. The fins 2304 and 2306 may be welded in position so that they do not come in contact with each other. While a combination of 16 fins is illustrated in FIGS. 23A-23E, a different number of fins may be used in other embodiments. As shown in FIG. 22, the catalytic coating may be directly coated on both sides of a supportive portion of the fins 2304 and/or 2306 or applied to a porous substrate (e.g., a foam or expanded nickel) which is affixed to the fins 2304 and/or 2306 using, e.g., spot-welding.

FIG. 23B shows a cross-sectional view of the interleaved current distribution parts 2300 along the longitudinal axis as indicated by A-B line 2310 of FIG. 23A. FIG. 23B shows the lateral section through a pair of the inner catalytically coated radial fins 2306 that are welded to the inner tube or rod 2308. FIG. 23C shows the lateral section through a pair of the outer catalytically coated radial fins 2304 that are welded to the wall 2302. Manifold components 2314 on both ends of the fins 2304 and 2306 positions and supports the fins 2304 and 2306 and tube or rod 2308. Power is supplied to the wall 2302 and the tube or rod 2308. The electrical contacts to the tube or rod 2308 and the wall 2302 are not shown in FIGS. 23B and 23C. In one example, power may be provided to the tube or rod 2308 in a fashion similar to that described with respect to FIGS. 18 and 19. A wave form at a frequency above DC may be applied as discussed above.

FIG. 23D shows a cross-sectional view of the manifold component 2314 perpendicular to the longitudinal axis as indicated by E-F line 2316 of FIG. 23B and G-H line 2318 of FIG. 23C. The material of the manifold components 2314 are chosen to withstand the operating conditions of the heated reaction vessel such as, e.g., temperatures above 350° C., while maintaining their insulation and strength capabilities. Examples of materials include high temperature, resistive plastic such as, e.g., Noryl, Bakelite and/or sintered

Teflon, among others. FIG. 23E is an end view the assembly including the interleaved current distribution parts 2300 and the manifold component 2314. Openings in the manifold component 2314 allow access to the fins 2304 and 2306. Since the fins 2304 and 2306 are monopolar electrodes, there is no danger of inter-electrode ionic shunting.

Disclosed herein are various embodiments related to electrochemical digestion of organic molecules. In an aspect, a method can comprise, for example, providing a fluid mixture including organic molecules to a reaction vessel including at least one current distribution part suspended within the fluid mixture and controlling an electrical potential applied to the at least one current distribution part to control current flow through the fluid mixture to heat the fluid mixture and simultaneously cause electrolysis of the fluid mixture. At least a portion of the current distribution part is coated with nano catalytic powders. In one or more aspects, the fluid mixture can be pumped continuously through the reaction vessel and/or the fluid mixture can be circulated through a holding tank and the reaction vessel. In various implementations, the nano catalytic powders can be less than 50 nm in diameter. The electrical potential can be applied to the at least one current distribution part in a square wave shape at a frequency below 1 Hz, at a frequency below 0.1 Hz, or at a frequency below 0.01 Hz. In some aspects, the method can further comprise sparging ozone into the fluid mixture. The fluid mixture can contain charge-carrying ions and/or the fluid mixture can include an ion source of the charge-carrying ions. For example, the ion source can be potassium hydroxide (KOH). In various embodiments, at least a portion of the fluid mixture can be selected from water, biomass, fossil fuels, seawater, contaminated fluids, slurries, emulsions, pastes, liquids, gases, plasmas, and combinations thereof and/or at least a portion of the fluid mixture can contains at least one of woody crops, herbaceous crops, the seeds of oil crops, and brown coal.

In other aspects, a device can comprise a pipe section distributed along a longitudinal axis of the device and surrounding a fluid mixture including organic molecules, a current distribution part positioned within the pipe section and suspended in the fluid mixture, and an electrical coupling assembly configured to provide an electrical potential to the current distribution part for heating and electrolysis of the fluid mixture. At least a portion of the current distribution part is coated with nano catalytic powders. In one or more aspects, the fluid mixture can be pumped continuously through the pipe section. The electrical potential can be applied to the at least one current distribution part in a square wave shape at a frequency below 1 Hz, at a frequency below 0.1 Hz, or at a frequency below 0.01 Hz. In various implementations, at least a portion of the pipe section is coated with nano catalytic powders. In some aspects, the current distribution part can comprise an inner conductive element extending along the longitudinal axis of the device and at least one intermediate conductive tube concentric with the inner conductive element and the pipe section. In various embodiments, an inner side and an outer side of the one intermediate conductive tube can be coated with nano catalytic powders. In various aspects, the current distribution part cab comprise an inner conductive element extending along the longitudinal axis of the device, where the inner conductive element including plates extending radially outward towards the pipe section. In some embodiments, the pipe section can include plates extending inward towards the longitudinal axis of the device, where the plates of the pipe section are interleaved with the plates of the current distribution part. In various implementations, the nano catalytic powders can be less than 50 nm in diameter.

In other aspects, a system can comprise a reaction vessel comprising conductive elements suspended in a fluid mixture including organic molecules, and a power source configured to supply an electrical potential to at least a portion of the conductive elements to heat the fluid mixture and simultaneously cause electrolysis of the fluid mixture. At least a portion of the conductive elements include a coating of nano catalytic powders. In various aspects, the system can further comprise a pump configured to continuously pump the fluid mixture through the reaction vessel and/or an ozone sparge configured to add ozone into the fluid mixture. In some implementations, the fluid mixture can be pumped continuously through the reaction vessel and/or the fluid mixture can be continuously circulated through a holding tank and the reaction vessel. The fluid mixture can contain charge-carrying ions and/or a source of the charge-carrying ions can be potassium hydroxide (KOH). The electrical potential can be applied to the at least one current distribution part in a square wave shape at a frequency below 1 Hz, at a frequency below 0.1 Hz, or at a frequency below 0.01 Hz. In various embodiments, at least a portion of the fluid mixture can be selected from water, biomass, fossil fuels, seawater, contaminated fluids, slurries, emulsions, pastes, liquids, gases, plasmas, and combinations thereof and/or at least a portion of the fluid mixture can contains at least one of woody crops, herbaceous crops, the seeds of oil crops, and brown coal. In various implementations, the nano catalytic powders can be less than 50 nm in diameter.

It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiment(s) without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.

It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a concentration range of “about 0.1% to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt % to about 5 wt %, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range. The term “about” can include traditional rounding according to significant figures of numerical values. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ to about ‘y’”. therefore, at least the following is claimed: 

1. A method, comprising: providing a fluid mixture including organic molecules to a reaction vessel including at least one current distribution part suspended within the fluid mixture, where at least a portion of the current distribution part is coated with nano catalytic powders; and controlling an electrical potential applied to the at least one current distribution part to control current flow through the fluid mixture to heat the fluid mixture and simultaneously cause electrolysis of the fluid mixture.
 2. The method of claim 1, wherein the fluid mixture is pumped continuously through the reaction vessel.
 3. The method of claim 1, wherein the nano catalytic powders are less than 50 nm in diameter.
 4. The method of claim 1, wherein the electrical potential is applied to the at least one current distribution part in a square wave shape at a frequency below 1 Hz.
 5. The method of claim 4, wherein the electrical potential is applied to the at least one current distribution part in a square wave shape at a frequency below 0.1 Hz.
 6. The method of claim 5, wherein the electrical potential is applied to the at least one current distribution part in a square wave shape at a frequency below 0.01 Hz.
 7. The method of claim 1, further comprising sparging ozone into the fluid mixture.
 8. The method of claim 1, wherein the fluid mixture contains charge-carrying ions.
 9. The method of claim 8, wherein the fluid mixture includes an ion source of the charge-carrying ions.
 10. The method of claim 1, wherein at least a portion of the fluid mixture is selected from the group consisting of water, biomass, fossil fuels, seawater, contaminated fluids, slurries, emulsions, pastes, liquids, gases, plasmas, and combinations thereof.
 11. The method of claim 1, wherein at least a portion of the fluid mixture contains at least one member of a group consisting of woody crops, herbaceous crops, the seeds of oil crops, and brown coal.
 12. A device, comprising: a pipe section distributed along a longitudinal axis of the device, the pipe section surrounding a fluid mixture including organic molecules; a current distribution part positioned within the pipe section, at least a portion of the current distribution part coated with nano catalytic powders, the current distribution part suspended in the fluid mixture; and an electrical coupling assembly configured to provide an electrical potential to the current distribution part for heating and electrolysis of the fluid mixture.
 13. The device of claim 12, wherein the fluid mixture is pumped continuously through the pipe section.
 14. The device of claim 12, wherein the electrical potential is applied to the current distribution part in a square wave shape at a frequency below 0.1 Hz.
 15. The device of claim 14, wherein the potential is applied in a square wave shape at a frequency below 0.01 Hz.
 16. The device of claim 12, wherein at least a portion of the pipe section is coated with nano catalytic powders.
 17. The device of claim 12, wherein the current distribution part comprises an inner conductive element extending along the longitudinal axis of the device and at least one intermediate conductive tube concentric with the inner conductive element and the pipe section.
 18. The device of claim 17, wherein an inner side and an outer side of the one intermediate conductive tube is coated with nano catalytic powders.
 19. The device of claim 12, wherein the current distribution part comprises an inner conductive element extending along the longitudinal axis of the device, the inner conductive element including plates extending radially outward towards the pipe section; and where the pipe section includes plates extending inward towards the longitudinal axis of the device, the plates of the pipe section interleaved with the plates of the current distribution part.
 20. The device of claim 12, wherein the nano catalytic powders are less than 50 nm in diameter. 